ENCRES D'IMPRESSION INSENSIBLES A L'ABRASION

ABRASION RESISTANT PRINTING INKS

Abrégé anglais

Printing inks comprising a pigment and an aqueous or non-aqueous solvent (or a
mixture of such solvents) have reduced
abrasiveness towards printing surfaces (e.g. gravure printing cylinders) by
incorporation in the ink of an alkoxylated dibasic
phosphate ester and at least one alkali metal salt of a diaikylsuifosuccinic
ester.

Revendications

8
WHAT IS CLAIMED IS:
1. A printing ink comprising a pigment and an aqueous or non-aqueous solvent
or a mixture of such solvents and having reduced abrasiveness towards printing
surfaces characterized in that the ink contains an alkoxylated dibasic
phosphate ester
and at least one alkali metal salt of a dialkylsulfosuccinic ester said
alkoxylated
dibasic phosphate ester being present in an amount 2 - 6 weight %, based on
the
weight of the printing ink, and said alkali metal salt of a
dialkylsulfosuccinic ester
being present in an amount of about 0.5 - 3 weight %, based on the weight of
the
printing ink.
2. The printing ink of claim 1 wherein the alkoxyl moiety of the alkoxylated
dibasic phosphate ester contains 2 - 8 carbon atoms.
3. The printing ink of claim 2 wherein the alcohol moiety of the alkoxylated
dibasic phosphate ester contains 5 - 10 carbon atoms.
4. The printing ink of claim 1 wherein the alkali metal comprises sodium and
the
alkyl moiety of the dialkylsulfosuccinic ester contains 8 -16 carbon atoms.
5. The printing ink of claim 4 wherein the dialkylsulfosuccinic ester
comprises a
mixture of two different dialkylsulfosuccinic esters.
6. The printing ink of claim 5 wherein the dialkyl moieties of one
dialkylsulfosuccinic ester are branched ethylhexyl groups and the dialkyl
moieties of
the other dialkylsulfosuccinic ester are tridecyl groups.

Description

WO 93/10198 PCT/US92109824
~~STGN $SISTANT F'~IN~NG INKS
Field of the Invention
The invention relates to printing inks which
exhibit reduced abrasiveness towards printing surfaces
such as gravure cylinders. The printing inks will
contain the usual pigment and aqueous or non-aqueous
solvent for mixture of such solvents) along with desired
binders, fillers, waxes, etc. The printing inks of the
present invention exhibit reduced abrasiveness as a
result of incorporation therein of an alkoxylated dibasic
phosphate ester and at least one alkali metal salt of a
dialkylsulfosuccinic ester.
ground of the Invention
Abrasion by printing ink on printing ink surfaces
has continued to plague the industry. The problem is
most severe in the case of gravure printing wherein after
long printing runs, the surfaces of the doctor blade and
the gravure cylinder wear out. This in turn causes
"hazing" or "scumming", i.e. printing in the non-image
areas. The phenomenon is particularly acute when water-
based inks are used in place of non-aqueous inks.
Environmental, health and safety considerations dictate
that, to the extent possible, solvents such as
hydrocarbons, alcohols, glycols, glycol ethers, ketones
and esters be replaced with water. Thus, solving the
abrasion problean would provide a greater incentive to
printers to utilize water-based inks.
Abrasion of the printing surfaces is, no doubt,
related to factors such as the type of pigment, pigment
crystal morphology, pigment particle size, etc. It is
thought that watex provides less lubricity than solvents.
However, incorporation of materials thought in the prior

WO 93/10198 PCT/US92/09824
'~.c~l~Nt> _2_
art to provide lubricity such as waxes, stearates, etc.
have had little effect in reducing the abrasion caused by
water-based inks after long printing runs.
It has now been discovered that the abrasiveness of
both aqueous and non-aqueous printing inks towards
printing surfaces is significantly reduced if an
alkoxylated dibasic phosphate ester and at least one
alkali metal salt of a dialkylsulfosuccinic ester are
incorporated in the ink.
Preferably, the alkoxyl moiety of the alkoxylated
dibasic phosphate ester contains 2 - 8, most preferably
4 - 6, carbon atoms, and the alcohol moiety of the
alkoxylated dibasic phosphate ester contains 5 - 10, most
preferably 7 - 10 carbon atoms, e.g. aromatic alcohol
groups. The alkoxylated dibasic phosphate:ester is
generally present in an amount of about 2 - 6, preferably
3 - 5, wt.%, based on the weight of the printing ink.
The alkali metal salt of the dialkylsulfosuccinic
ester preferably comprises sodium, and each dialkyl
moiety contains 8 - 16, preferably 8 - 13 carbon atoms.
Most preferably, the dialkylsulfosuccinic ester comprises
a mixture of two different dialkylsulfosuccinic esters,
one in which the dialkyl moieties are branched chain
ethylhexyl groups, and the other in which the dialkyl
moieties are tridecyl. Generally, the total amount of
all alkali metal salts of the dialkylsulfosuccinic
esterts) will be in the range of about 0.5 - 3,
preferably 0.8 - 1.5, wt.%, based on the weight of the
printing ink.

WO 93/10198
PCT/US92/09824
As indicated in the Examples presented below,
incorporation of the phosphate ester or the sulfosuccinic
ester alone results in no significant reduction in
abrasiveness. Both the phosphate ester and the
sulfosuccinic ester are required and especially good
results are achieved if equal amounts of two different
sulfosuccinic esters, rather than a single sulfosuccinic
ester, are employed in combination with the phosphate
ester. Further, the present invention is equally
effective in water-based printing inks, solvent-based
printing inks and printing inks containing both water and
non-aqueous solvents.
Apart from the present invention, the printing ink
components are conventional in nature. As indicated
above, the solvent may be water, non-aqueous solvents or
a mixture thereof.- Typical solvents include aliphatic
hydrocarbons, naphthenic hydrocarbons, aromatic
hydrocarbons (e.g. toluene, xylene), C~ - C' alcohols, C2
- C~Z glycols and glycol ethers, ketoses, esters, etc.
The pigment is conventional in nature and may be
any organic pigment used in printing inks or may be
inorganic in nature, e.g. monoarylide yellows, diarylide
yellows, pyra~olones, bezimidazolones, toluidine red,
naphthol red,.lithol rubines, phthalocyanine blue and
green, carbon blacks, titanium dioxide, zinc sulphide,
calcium carbonate, China clay, etc. Typically, the
:grinting,ink will also contain binders, e.g. rosins
and/or resins such as wood rosin, metallic resinates,
malefic-modified rosins and resins, phenolic resins, alkyd
resins, polyamide resins, acrylic and methacrylie resins,
etc. The printing ink may also contain oils (e.g. soy
bean oilj, plasticizers, natural and/or synthetic waxes,
driers, extenders, etc.
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WO 93/10198 PGT/US92/09824
_q_
The laboratory test used to evaluate the
abrasiveness of a printing ink involves the following
procedure: 20 g of the printing ink is placed in a tray
and a chromium-coated glass is immersed in the ink. A
felt-covered weight is rubbed against the glass for a
fixed number of strokes. The abrasiveness of the ink is
then determined as a function of the amount of chromium
coating removed from the glass.
The invention may be better understood by reference
to the following examples: all parts are by weight or
wt.% unless otherwise indicated.
A water based ink was formulated from the follpwing
materials:
Material y ~Tt~,%
Zinc sulphide 40
Acrylic emulsion° 15
Acrylic resin solutionb 25
Ethylene glycol monopropyl ether 5
Water 13
Ammonia 2
° This emulsion consisted of emulsified styrene-
acrylic copolymer of about 200,000 mol. wt, and about 40%
solids.
b This solution consisted of styrene-acrylic
copolymer of about 10,000 mol. wt, neutralized with
~~ ammonia and about 40% solids.
After 3,000 rubs in the abrasion tester, the
abrasion produced by this printing ink formulation was
rated 7 on a scale of 1 to 10 (10 being the worst).
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a=..~. .w ,...r ... . . ..~

WO 93/10198 PCT/US92/09$24
~1~.~~.~~~
E_ xample a
The ink of Example 1 was reformulated by the
addition of 4% of a phosphate ester composition
consisting of a mixture of a nonoxy phenoxy ethoxylated
phosphate and a heptyl ethoxylated phosphate in about an
80:20 ratio. After 3,000 rubs in the abrasion tester,
the abrasion produced by this ink formulation was rated 4.
The ink of Example 1 was reformulated by the
addition of 2% of sodium 2-ethylhexyl sulfosuccinate and
tested by the same method as above; this ink was rated 6
after 3,000 rubs.
Exav
Example 3 was repeated using 2% of sodium tridecyl
sulfosuccinate; this ink was rated 6 after 3,000 rubs.
Example 3 was repeated using a mixture of 1% of
sodium 2-ethylhexyl sulfosuccinate and 1% of sodium
tridecyl sulfosuccinate; this ink was rated 4 after 3,000
rubs.
;~xamDle 6
The ink of Example 1 was reformulated by the
addition of 4% of a phosphate ester composition
consisting of a mixture of a nonoxy phenoxy ethoxylated
phosphate and a heptyl ethoxylated phosphate in about an
80:20 ratio and 2% of sodium 2-ethylhexyl sulfosuccinate;
this ink was rated 3 after 3,000 rubs.

CA 02119120 2002-11-21
-6-
The ink of Example 1 was reformulated by the
addition of 4% of a phosphate ester composition
consisting of a mixture of a nonoxy phenoxy ethoxylated
phosphate and a heptyl ethoxylated phosphate in about an
80:20 ratio, 1% of sodium 2-ethylhexyl sulfosuccinate and
1% of sodium tridecyl sulfosuccinate: this ink was rated
1 after 3,000 rubs.
A printing ink base was prepared from 15% "Printex
45" carbon black (a type of carbon black typically used
in solvent-based grawre printing inks), 3% "Soleate DO";
a standard oleic acid ester wetting agent, 70% Gilsonite.*
varnish (a natural resin) and 12% toluene. These
materials were ground for about 2 hours with 3 mm glass
shots and the resultant ground dispersion was then
diluted to final ink viscosity, as follows: 50% ink
base, 45% calcium/zinc resinate varnish and 5% toluene:
this ink resulted in a chrome wear of 0.3~. A second ink
was prepared in which the "Soleate DO"*wetting agent was
replaced with 3% sodium 2-ethylhexyl sulfosuccinate; the
second ink resulted in a chrome wear of 0.~.~. A third
ink was prepared in which the "Soleate DO"*wetting agent
was replaced with 3% sodium 2-ethylhexyl sulfosuccinate
and 1% of a phosphate ester composition consisting of a
mixture of a nonoxy phenoxy ethoxylated phosphate and a
heptyl ethoxylated phosphate in about an 80:20 ratio: the
third ink resulted in a chrome wear of 0.05~C.
The three inks were then trialled on a commercial
high speed grawre printing press. The trials indicated
that the additives of the present invention solved the
abrasiveness problem associated with conventional inks.
* Trade marks

PCf/ US92/09824
'u0 93/10198
_7_
These trials also proved that the additives of the
present invention are equally effective in solvent based
inks.